Cluster Structure of Rare Earth Doped Fluorite Halide Crystals

Abstract

Abstract: Rare earth doped fluorite halides play important roles in the fields of economy, national defense, and so on. The trivalent rare earth ions easily cluster in fluorite halides due to the special crystal structure. However, the systematic investigation into the aggregation of rare earth ions is rarely reported. In this work, the cluster structure characteristics, evolution patterns and their connections, as well as the influencing factors were systematically studied. It is found that the stabilities of 1|0|0|1₁ (C_4v) and 1|0|0|1₂ (C_3v) rare earth monomers vary with the ionic radius, and the trends are different in different matrix crystals, which are consistent with the analysis of lattice distortion. The coupling of lattice distortion and coulomb interactions determines the site occupations of charge compensation interstitial halide ions, i.e. the relative stabilities of C_4v and C_3v center. Additionally, the covalent effect makes the monomer structures of rare earth doped PbF₂ and SrCl₂ are different from that of CaF₂, SrF₂ and BaF₂. The study also reveals the relationship of energy difference slopes of monomers with crystal ionicity and cell size. The structures of high-order rare earth clusters were also studied and its evolutions are intimately related with that of monomer centers. The criterion of relative stabilities in high-order clusters is proposed, which provides a guideline for the exploration, screening and development of new rare earth doped fluorite halides, and its application scope is highly expected to be extended.

Key words: fluorite halide crystal, rare earth ion cluster, structure evolution, lattice distortion, high-order cluster

CLC Number:

O734
O641

MA Fengkai, ZHANG Zhen, JIANG Dapeng, ZHANG Zhonghan, LI Zhen, KOU Huamin, CHEN Zhenqiang, SU Liangbi. Cluster Structure of Rare Earth Doped Fluorite Halide Crystals[J]. Journal of Synthetic Crystals, 2023, 52(7): 1219-1235.

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